Electrical Doping Research Articles

Electrical Doping Regulation of Carrier Recombination Enhances the Perovskite Solar Cell Efficiency beyond 28.

With the power conversion efficiency (PCE) of perovskite solar cells (PSCs) exceeding 26.7%, achieving further enhancements in device performance has become a key research focus. Here, we investigate the impact of electrical doping in the perovskite layer using the drift-diffusion equation-based device physics model, coupled with a self-developed equivalent circuit model. Our results demonstrate that electrical doping can increase the PCE from 24.78% to >28%. In-depth theoretical analysis reveals that these improvements in performance are driven by the modulation of carrier recombination processes through doping, leading to significant increases in the open-circuit voltage and fill factor. Additionally, we explore the influence of physical parameters on device performance. Our study identifies an optimal doping concentration range from 1.0 × 1017 to 1.0 × 1019 cm-3 and a transport layer mobility of >0.01 cm2 V-1 s-1. This work provides a theoretical foundation for the development of ultra-high-performance PSCs through targeted electrical doping strategies.

Electrical Doping in Sc-III-Nitrides: Toward Multifunctional Devices at the Signal Device Level.

A homogeneous integration of various types of devices using a single material platform is an ideal route toward multifunctional devices at the single-device level for miniaturized, fast, and energy-efficient systems. However, such a single material platform is still missing. Scandium-containing III-nitrides (Sc-III-nitrides) are promising, but their electrical doping properties remain unknown. In this work, the electrical doping in Sc-III-nitrides is investigated and optoelectronic devices using Sc-III-nitrides on silicon (Si) are further demonstrated. The material format of the nanowire is used, with magnesium (Mg) serving as the impurity dopant to control the electrical doping. It is discovered that, by adjusting the Mg doping concentrations, the Sc-III-nitrides can be tuned from n-type to p-type. Device application in light-emitting is further demonstrated using the p-type Sc-III-nitrides as the hole injection layer. The performance comparison between devices using the regrown Sc-containing p-type contact layers and non-Sc-containing p-type contact layers indicates the advantage of Sc incorporation in improving the quality of the regrown p-type layer in a device structure. The electrical doping in Sc-III-nitrides demonstrated in this study represents an important step toward a homogeneous integration of different types of devices using a single material platform.

Electrical Control of Valley Polarized Charged Exciton Species in Monolayer WS2.

Excitons are key to the optoelectronic applications of van der Waals semiconductors, with the potential for versatile on-demand tuning of properties. Yet, their electrical manipulation remains challenging due to inherent charge neutrality and the additional loss channels induced by electrical doping. We demonstrate the dynamic electrical control of valley polarization in charged excitonic states of monolayer tungsten disulfide, achieving up to a 6-fold increase in the degree of circular polarization under off-resonant excitation. In contrast to the weak direct tuning of excitons typically observed using electrical gating, the charged exciton photoluminescence remains stable, even with increased scattering from electron doping. By exciting at the exciton resonances, we observed the reproducible nonmonotonic switching of the charged state population as the electron doping is varied under gate bias, indicating a resonant interplay between neutral and charged exciton states.

The increase of the scattering at high electric fields in multilayer ReS2 FETs: Output characteristics and 1/f noise

Field-effect transistors (FETs) employing two-dimensional (2D) materials have attracted significant attention as a potential alternative to silicon FETs. Among these materials, multilayer rhenium disulfide (ReS2) has emerged as a focal point of interest owing to its distinctive direct bandgap properties. While there is extensive research on the electrical characteristics and doping, studies on the changes in electrical properties during scale-down for practical applications are insufficient. In this study, we investigated the mobility reduction of ReS2 FETs at high drain bias of ReS2 FETs by comparing the different channel lengths of 0.24 μm and 1.5 μm. A reduction in mobility was observed for the shorter channel length, attributed to the enhanced scattering factor at high electric field. To assess the impact of scattering degradation, we conducted a low-frequency noise analysis at drain-source voltage (VDS) = 0.4 V and VDS = 3.0 V for the 0.24 μm length FET. The decrease of the Hooge parameter (αH) at high VDS was observed, which was attributed to an augmentation in Coulomb scattering. This study observed mobility degradation under high electrical fields during scale-down and identified the cause of mobility degradation through low-frequency noise analysis. This contributes to scaling down for practical applications of 2D FETs.

(Invited) Doping at the Extreme in Organic Semiconductors: Challenges and Opportunities

Molecular doping is an effective tool to enhance bulk conductivity, increase carrier injection and de-activate electron or hole traps in organic molecular and polymer semiconductors. Considerable effort has been directed toward the synthesis of powerful and stable p-type and n-type molecular dopants over the past decade.[1,2] This talk reviews a range of molecular redox agents used in organic electronics, with focus on strong reductants and oxidants for organic semiconductors with low electron affinity (EA) and large ionization energy (IE), respectively. In particular, we look at air-stable dimers, e.g. [RuCp*Mes]2, formed of 19-electron organometallic sandwich compounds able to reduce organic semiconductors with EA well below 3 eV.[3] We review powerful single-electron molecular oxidants, e.g. F6-TCNNQ and CN6-CP, which can introduce holes in organic semiconductors with IE larger than 5.6 eV. Applications of these n- and p-dopants to improve the conductivity of carrier injection layers and create large gap semiconductor p-i-n structures are described.[4] The last part of the talk focuses on recent work on adduct-based p-doping of organic semiconductors, applicable to a range of hole transport materials.[5][1]S. Barlow, S.R. Marder, X. Lin, F. Zhang and A. Kahn, Electrical Doping of Organic Semiconductors with Molecular Oxidants and Reductants, Handbook of Conducting Polymers (2019)[2] G. Song, S.B. Kim,S. Mohapatra, Y. Qi, T. Sajoto, A. Kahn, S.R. Marder, S. Barlow, n-Doping of Organic Electronic Materials Using Air-Stable Organometallics, Adv. Mat. 24, 699 (2012)[3] X. Lin, B. Wegner, K. M. Lee, M. A. Fusella, F. Zhang, K. Moudgil, B. P. Rand, S. Barlow, S. R. Marder, N. Kochand A. Kahn, Beating the Thermodynamic Limit: Photo-Activation of n-Doping in Organic Semiconductors, Nature Materials 16, 1209 (2017)[4] H. L. Smith, J. T. Dull, S. Mohapatra, S. Barlow, S. Marder, B. P. Rand, and A. Kahn, Powerful organic molecular oxidant and reductant enable a large gap, blue light-emitting organic homojunction diode, ACS Appl. Mat. Int. 14, 2381 (2022)[5] N. Sakai, R. Warren, F. Zhang, S. Nayak, S. V. Kesava, Y.-H. Lin, H. S. Biswal, X. Lin, A. Kahn, M. Riede, P. K. Nayak and H. J. Snaith, Adduct-based p-doping of Organic Semiconductors, Nature Materials, 20, 1248 (2021)

Reaction mechanisms for electrical doping of organic semiconductors using complex dopants

Reaction mechanisms for electrical doping of organic semiconductors using complex dopants

N-type molecular doping of a semicrystalline conjugated polymer through cation exchange

Control of electrical doping is indispensable in any semiconductor device, and both efficient hole and electron doping are required for many devices. In organic semiconductors, however, electron doping has been essentially more problematic compared to hole doping because in general organic semiconductors have low electron affinities and require dopants with low ionization potentials that are often air-sensitive. Here, we adapt an efficient molecular doping method, so-called ion-exchange doping, to dope electrons in a polymeric semiconductor. We initially reduce the polymeric semiconductor using one electron transfer from molecular dopants, and then the ionized dopants in the resulting air-unstable films are replaced with secondary ions via cation exchange. Improved ambient stability and crystallinity of the doped polymeric semiconductors are achieved when a specific bulky molecular cation was chosen as the secondary ion, compared to conventional methods. The presented strategy can overcome the trade-off relationship between reducing capability and ambient stability in molecular dopants, and a wider selection of dopant ions will help to realize ambient-stable electron conductors.

Electrical Doping of Metal Halide Perovskites by Co-Evaporation and Application in PN Junctions.

Electrical doping of semiconductors is a revolutionary development that enabled many electronic and optoelectronic technologies. While doping of many inorganic and organic semiconductors is well-established, controlled electrical doping of metal halide perovskites (MHPs) is yet to be demonstrated. In this work, efficient n- and p-type electrical doping of MHPs by co-evaporating the perovskite precursors alongside organic dopant molecules is achieved. It is demonstrated that the Fermi level can be shifted by up to 500 meV toward the conduction band and by up to 400 meV toward the valence band by n- and p-doping, respectively, which increases the conductivity of the films. The doped layers are employed in PN and NP diodes, showing opposing trends in rectification. Demonstrating controlled electrical doping by a scalable, industrially relevant deposition method opens the route to developing perovskite devices beyond solar cells, such as thermoelectrics or complementary logic.

Observation of a Chern insulator in crystalline ABCA-tetralayer graphene with spin-orbit coupling.

Degeneracies in multilayer graphene, including spin, valley, and layer degrees of freedom, can be lifted by Coulomb interactions, resulting in rich broken-symmetry states. Here, we report a ferromagnetic state in charge-neutral ABCA-tetralayer graphene driven by proximity-induced spin-orbit coupling from adjacent tungsten diselenide. The ferromagnetic state is identified as a Chern insulator with a Chern number of 4; its maximum Hall resistance reaches 78% quantization at zero magnetic field and is fully quantized at either 0.4 or -1.5 tesla. Three distinct broken-symmetry insulating states, layer-antiferromagnet, Chern insulator, and layer-polarized insulator, along with their transitions, can be continuously tuned by the vertical displacement field. In this system, the magnetic order of the Chern insulator can be switched by three knobs, including magnetic field, electrical doping, and vertical displacement field.

Dramatically Enhanced Light‐Emitting/Detecting Bifunction of CH3NH3PbBr3 Single‐Crystal Thin‐Film via Electrical Doping‐Induced Defects Passivation

AbstractHigh‐performance light‐emitting/detecting bifunctional optoelectronic devices based on halide perovskites are hindered by the less efficient carrier transport and radiative recombination processes. The density of defects (i.e., surface and bulk defects) is the main factor affecting carrier transport, radiation recombination, and determining performance in perovskites. Therefore, techniques to effectively regulate defects are highly needed. Here, a convenient and effective strategy, electrical doping, is proposed to flexibly regulate defect density, resulting in dramatically enhanced light‐emitting (i.e., fluorescence and carrier lifetime) and light‐detecting performance (i.e., hole mobility, photo‐responsivity, and photo‐detectivity) simultaneously. An improved carrier transport model in CH3NH3PbBr3 (MPB) single‐crystal thin‐film (SCTF) is proposed to elucidate the regulation mechanism of defects and carrier transport under electrical doping. These results show that the surface defect density can be effectively reduced by 47.49% under optimal electrical poling intensity (0.168 V µm−1), and photoluminescence intensity and carrier lifetime can be increased by 259% and 89.98%, respectively. Furthermore, planar MPB SCTF photodetector exhibits hole mobility increased by 14.97%, photo‐responsivity increased by 82.78%, and photo‐detectivity increased by 868% at 0.168 V µm−1. Particularly, a record photo‐detectivity of 3.53 × 1013 Jones is achieved under electrical doping. This study provides guidance for flexibly adjusting defect density and optimizing perovskite SCTFs light‐emitting/detecting bifunctional devices.

Influence of N-type electron acceptors in perovskite absorbers for stabilized perovskite absorbers for high-performance perovskite solar cells

In this study, the impact of n-type organic electron acceptors incorporated in perovskite absorbers via antisolvent-assisted crystallization process is investigated on optical, electrical, and photovoltaic properties of perovskite solar cells (PSCs). The study examines the effect of three representative electron acceptors, including fullerene derivative (PC61BM), non-fullerene acceptor (ITIC), and fluorinated non-fullerene acceptor (ITIC-4F). The findings demonstrate that the inclusion of these electron acceptors stabilizes perovskite absorbers due to strong interaction between the organic acceptors and [PbI6]4- octahedra, leading to the successful passivation of defective antisites. Furthermore, ITIC-4F plays a crucial role in the tailored electronic structure of the perovskite absorber surface, facilitating efficient charge transport and suppressing carrier recombination in the device. The synergetic effect of defect passivation and electrical doping achieved by ITIC-4F resulted in an efficiency improvement of 17.31 % of MAPbI3-based PSCs under 1-Sun illumination, exceeding that of the pristine device (15.62 %) under the same conditions. The device passivated with ITIC-4F also delivered an efficiency of 20.00 % under dim-light irradiation conditions for indoor photovoltaic applications. The results highlight the potential of n-type organic semiconducting molecules as effective additives in the antisolvent-assisted crystallization of perovskite absorbers, offering valuable insights into the design of organic semiconducting additives for improving the film quality of perovskite absorbers and achieving high-performance PSCs. The findings provide a foundation for future research aimed at enhancing the optoelectronic properties and photovoltaic performance of PSCs.

Structural insight into nanoscale inhomogeneity of electrical properties in highly conductive polycrystalline ZnO thin films doped using methane

Recently, methane has been demonstrated as an effective n-type dopant for ZnO thin films deposited using the RF-magnetron sputtering method. It was shown that the major electrical doping effect of methane is caused by hydrogen released during methane decomposition. This work investigates the origin of the observed increase in conductivity of methane-doped ZnO films with the increase in thickness. The study is aimed at describing the nature of this thickness-dependent effect through a detailed analysis of the thickness-dependent morphology and crystalline structure. A combination of structural, electrical, and optical characterization revealed a transition from fine-grained films with a random orientation at early stages to partially (002)-textured films with columnar grains at later stages of growth. It is demonstrated that grain/sub-grain boundaries increase the electrical conductivity and that the contribution of such buried inner boundaries increases with increasing thickness. It is proposed that hydrogen diffuses along the grain and sub-grain boundaries during growth, leading to continuous doping of the buried interfaces. This hydrogen diffusion mechanism results in an apparent ‘additional doping’ of thicker films. The results provide new insights into the thickness-dependent conductivity of doped polycrystalline ZnO films mediated by hydrogen diffusion along internal interfaces.

Solution-based electrical doping of organic photovoltaics with non-fullerene acceptors facilitated by solvent vapor pre-treatment

Solution-based electrical doping of organic semiconductors using 12-molybdophosphoric acid (PMA) hydrate has been shown to allow p-type doping of conjugated polymers over a limited depth from the surface, enabling the fabrication of organic solar cells with a simplified device architecture. However, the doping level of certain conjugated polymers using PMA was found to be limited by the polymer film volume. Here, we report a modified PMA doping technique based on film volume expansion that is applicable to device fabrication, leading to hole-collecting layer-free non-fullerene organic photovoltaic devices, which exhibit a comparable photovoltaic performance to those with a commonly evaporated MoO3 hole-collecting layer.

Graphene-boosted ultra-wide band reconfigurable optical switch for SOI-based telecom applications: A numerical study

In this work, we propose the design of a compact optical switch featuring a wide bandwidth of 360 nm, suitable for telecom operations. The switch is a passive 3dB splitter realized through a Y-branch, electrically activated via a graphene/insulator/graphene (GIG) capacitor embedded within the rib waveguide (WG). The capacitor itself is embedded within an SOI-based hybrid WG composed of crystalline (c-Si) and hydrogenated amorphous silicon (a-Si:H), with the GIG between the two layers. Such a photonic structure optimizes the light-matter interaction and enables a compact device with a length of only 100 μm. By applying a voltage bias to the graphene layers, we achieve the condition necessary for efficient data transmission through the WG. Indeed, the electrical doping of graphene enables the modulation of optical losses within the waveguide, ranging from total light absorption to up to 70% transmission. The simplicity and ease of fabrication of this innovative design offer significant advantages for integration into existing photonic circuits. Its wide bandwidth allows compatibility with a variety of telecom wavelengths, providing flexibility in network configurations. Consequently, this compact optical switch presents a promising solution for modern data communication needs, demonstrating a balance between efficiency and scalability.

Inside Front Cover

In this critical review, the authors explore electrical doping strategies of metal‐halide perovskites, which remains as a fundamental challenge. These challenges can potentially become a key to achieving efficient thermoelectric energy generation with this emerging class of materials. image

Improving Strain-localized GaSe Single Photon Emitters with Electrical Doping.

Exciton localization through nanoscale strain has been used to create highly efficient single-photon emitters (SPEs) in 2D materials. However, the strong Coulomb interactions between excitons can lead to nonradiative recombination through exciton-exciton annihilation, negatively impacting SPE performance. Here, we investigate the effect of Coulomb interactions on the brightness, single photon purity, and operating temperatures of strain-localized GaSe SPEs by using electrostatic doping. By gating GaSe to the charge neutrality point, the exciton-exciton annihilation nonradiative pathway is suppressed, leading to ∼60% improvement of emission intensity and an enhancement of the single photon purity g(2)(0) from 0.55 to 0.28. The operating temperature also increased from 4.5 K to 85 K consequently. This research provides insight into many-body interactions in excitons confined by nanoscale strain and lays the groundwork for the optimization of SPEs for optoelectronics and quantum photonics.

Nonlinear Plasmonics in Nanostructured Phosphorene.

Phosphorene has emerged as an atomically thin platform for optoelectronics and nanophotonics due to its excellent optical properties and the possibility of actively tuning light-matter interactions through electrical doping. While phosphorene is a two-dimensional semiconductor, plasmon resonances characterized by pronounced anisotropy and strong optical confinement are anticipated to emerge in highly doped samples. Here we show that the localized plasmons supported by phosphorene nanoribbons (PNRs) exhibit high tunability in relation to both edge termination and doping charge polarity and can trigger an intense nonlinear optical response at moderate doping levels. Our explorations are based on a second-principles theoretical framework, employing maximally localized Wannier functions constructed from ab initio electronic structure calculations, which we introduce here to describe the linear and nonlinear optical response of PNRs on mesoscopic length scales. Atomistic simulations reveal the high tunability of plasmons in doped PNRs at near-infrared frequencies, which can facilitate the synergy between the electronic band structure and plasmonic field confinement to drive efficient high-harmonic generation. Our findings establish nanostructured phosphorene as a versatile atomically thin material candidate for nonlinear plasmonics.

Impact of Sm2O3 doping on PZT-PMI-PZS ternary ceramics: Phase structure, microstructure, and dielectric characteristics

This study aims to comprehensively evaluate the impact of Sm2O3 doping on PZT ceramics, specifically focusing on the phase structure, microstructure, and dielectric characteristics of Pb1-xSmx[(Zr0.52Ti0.48)0.9(Mo1/3In2/3)0.05(Zn1/3Sb2/3)0.05]O3 samples namely PSZT-PSMI-PSZS ceramics. Sm2O3 was doped at site A within the range of 0.00 ≤ x ≤ 0.08 using the solid-state reaction method and sintering at 1150 °C. The examination of the results revealed that the samples exhibited a perovskite structure, along with a secondary phase, with increasing intensity of the said phase as Sm content increased. XRD, Rietveld refinement, and Raman spectroscopy analysis indicate a decrease in the rhombohedral phase ratio (R) and an increase in the tetrahedral phase ratio (T) with higher Sm content. Microscopic examination using SEM demonstrates variations in microstructure, with the highest density and grain size observed at a small increment of Sm content (x ≤ 0.02). Optimal electrical properties were achieved at x = 0.00, including a high dielectric constant (εr = 8578), Curie temperature (Tc) of 303 °C, and dielectric loss (tanδ) value of 0.34. Conductivity studies indicate a negative temperature coefficient of resistance (NTCR) for all samples. Additionally, the relationship between electrical characteristics and Sm2O3 doping is discussed. This research provides valuable insights into the structural, microstructural, and electrical properties of PZT ceramics affected by Sm2O3 doping.

Inverted organic tandem solar cells with a charge recombination stack employing spatially confined p-type electrical doping

We report on the application of solution-based p-type electrical doping using 12-molybdophosphoric acid hydrate (PMA) to the fabrication of organic tandem solar cells. Such a doping approach leads to a spatially confined vertical doping profile down to a limited depth from the surface of polymer films, thus allowing the hole-collecting component of the charge recombination stack to be embedded in the photoactive layer of the bottom sub-cell. This simplifies the device architecture by removing the need for an extra dedicated hole-collecting layer. It is shown that this novel charge recombination stack comprising a PMA-doped bottom photoactive layer and a trilayer of Ag/AZO/PEIE is compatible with a solution-processed top photoactive layer. The fabricated inverted organic tandem solar cells exhibit an open-circuit voltage that is close to the sum of the open-circuit voltages of the individual sub-cells, and a fill factor that is close to the better fill factor of the two sub-cells.

Unlocking the potential of metal halide perovskite thermoelectrics through electrical doping: A critical review

AbstractOver the past decade, metal halide perovskites (MHPs) have received great attention, triggered by the tremendous success of their record‐breaking power conversion efficiency values in solar cells. Recently, there have been significant interests in fully utilizing their unique properties by exploring other device applications including thermoelectrics, which is promising due to their ultralow thermal conductivity and high mobility relative to their competitors among solution‐processable materials. However, the performance of MHP thermoelectrics reported so far falls significantly short of theoretical predictions, as the doping levels achieved to date are typically below the optimum values for maximizing the thermoelectric power factor, indicating the need for effective electrical doping strategies. In this critical review, recent studies aimed at enhancing the thermoelectric properties of MHPs are discussed, with a focus on the relatively under‐explored area of electrical doping in MHPs. The underlying charge transport mechanism and doping effect on transport are also examined. Finally, the challenges facing MHP thermoelectrics are highlighted, and potential research visions for achieving highly efficient thermoelectric conversion based on MHPs are offered.image